I've installed PHP 5.2 with Web PI on Windows Server 2008. This server also houses the Exchange server that I use for mail.
The script I'm using uses PHP's mail() function to send mail.
When using the function, mail is delivered when the recipient is within the domain, however if recipient is outside, it fails to deliver and mail returns an error.
I can't seem to find anything in the log files, so I am assuming it is an Exchange 2010 error.
Does your PHP script give you an error? I would imagine you're being denied relay access, but that's purely a guess.
You can verify if you're being denied relay pretty quickly by sending a mail using telnet. The place you're going to be told you're denied relay access is after the RCPT TO command.
If you are being denied relay, you will need to grant this (unfortunately I've not played with Exchange 2010, but I imagine it's similar to previous versions where you can authorise an IP address).